We explore the feasibility of principal component analysis (PCA) as a form of spectral imaging in photon-counting CT. Using the data acquired by a prototype system and simulated by computer, we investigate the feasibility of spectral imaging in photon-counting CT via PCA for feature extraction and study the impacts made by data standardization and de-noising on its performance. The PCA in the projection domain maintains the data consistence that is essential for tomographic image reconstruction and performs virtually the same as that in the image domain. The first three primary components account for more than 99.99% covariance of the data. Within anticipation, the contrast-to-noise ratio (CNR) between the target and background in the first principal component image can be larger than that in the image generated from the data acquired in each energy bin. More importantly, the CNR in the first principal component image may be larger than that in the image formed by the summed data acquired in all energy bins (i.e., the conventional polychromatic CT image). In addition, de-noising can not only reduce the noise in images but also improve the effectiveness/efficiency of PCA in feature extraction. The PCA in either projection or image domain provides another form of spectral imaging in photon-counting CT that fits the essential requirements on spectral imaging in true color. The verification of PCA's feasibility in CT as a form spectral imaging and observation of its potential superiority in CNR over conventional polychromatic CT are meaningful in theory and practice.